Anthraquinone-2-Sulfonate as a Microbial Photosensitizer and Capacitor Drives Solar-to-N 2 O Production with a Quantum Efficiency of Almost Unity.

Semiartificial photosynthesis shows great potential in solar energy conversion and environmental application. However, the rate-limiting step of photoelectron transfer at the biomaterial interface results in an unsatisfactory quantum yield (QY, typically lower than 3%). Here, an anthraquinone molecule, which has dual roles of microbial photosensitizer and capacitor, was demonstrated to negotiate the interface photoelectron transfer via decoupling the photochemical reaction with a microbial dark reaction. In a model system, anthraquinone-2-sulfonate (AQS)-photosensitized Thiobacillus denitrificans , a maximum QY of solar-to-nitrous oxide (N 2 O) of 96.2% was achieved, which is the highest among the semiartificial photosynthesis systems. Moreover, the conversion of nitrate into N 2 O was almost 100%, indicating the excellent selectivity in nitrate reduction. The capacitive property of AQS resulted in 82-89% of photoelectrons released at dark and enhanced 5.6-9.4 times the conversion of solar-to-N 2 O. Kinetics investigation revealed a zero-order- and first-order- reaction kinetics of N 2 O production in the dark (reductive AQS-mediated electron transfer) and under light (direct photoelectron transfer), respectively. This work is the first study to demonstrate the role of AQS in photosensitizing a microorganism and provides a simple and highly selective approach to produce N 2 O from nitrate-polluted wastewater and a strategy for the efficient conversion of solar-to-chemical by a semiartificial photosynthesis system.